CN108026268A

CN108026268A - Aromatic polyester, aromatic polyester liquid composition, the manufacture method of aromatic polyester film and aromatic polyester film

Info

Publication number: CN108026268A
Application number: CN201680051592.7A
Authority: CN
Inventors: 杉山贵之; 伊藤丰诚
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2015-09-09
Filing date: 2016-09-05
Publication date: 2018-05-11
Anticipated expiration: 2036-09-05
Also published as: US10787570B2; US20180355171A1; WO2017043439A1; CN108026268B; JP6112750B1; TWI705088B; EP3348597A4; TW201723021A; EP3348597A1; JPWO2017043439A1; EP3348597B1; KR102556587B1; KR20180050308A

Abstract

A kind of aromatic polyester, as Component units, it includes：(A) repetitive unit in aromatic amine source and the repetitive unit in (D) aromatic diol source in the aromatic amine of the repetitive unit represented by following formula (a), the repetitive unit in (B) aromatic dicarboxylic acid source, (C) selected from aromatic diamine and with hydroxyl；Relative to (A) to (D) repetitive unit it is total, (A) containing ratio of repetitive unit is 10 moles of % less than 20 moles of %, (B) containing ratio of repetitive unit is more than 40 moles of % and is 45 moles of below %, (C) repetitive unit and total containing ratio of the repetitive unit of (D) more than 40 moles of % and is 45 moles of below %, and the containing ratio of the repetitive unit of (D) more than 0 mole of % and is less than 15 moles of %.‑O‑Ar¹In CO (a) formulas, Ar¹Represent 1,4 phenylenes, 2,6 naphthylenes or 4,4 ' biphenylenes；Ar¹At least one hydrogen atom in represented group is optionally separately substituted by halogen atom, alkyl or aryl.

Description

Aromatic polyester, aromatic polyester liquid composition, the manufacturer of aromatic polyester film Method and aromatic polyester film

Technical field

The present invention relates to aromatic polyester, aromatic polyester liquid composition, the manufacture method of aromatic polyester film and virtue Fragrant race's polyester film.

The application CLAIM OF PRIORITY based on the Patent 2015-177737 in Japan's proposition on the 9th of September in 2015, and will Its content is applied at this.

Background technology

Aromatic polyester shows excellent high frequency characteristics, agent of low hygroscopicity, therefore studies its film as electric substrate etc. The application of material.

For example, Patent Document 1 discloses a kind of aromatic polyester, including above-mentioned aromatic polyester and N- crassitudes The aromatic polyester liquid composition of the non-protonic solvents such as ketone, wherein, which includes (A) aromatic series of ormal weight The repetitive unit in hydroxycarboxylic acid source, the repetitive unit in (B) aromatic dicarboxylic acid source, (C) are selected from aromatic diamine and have The repetitive unit in the aromatic amine source in the aromatic amine of hydroxyl, in addition, patent document 1 is also disclosed by combining liquid Thing is cast on supporting substrates, then removes solvent the manufacture method of aromatic polyester film implemented.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2004-315678 publications

The content of the invention

The subject that the invention solves

However, as the film that the aromatic polyester described in above patent document 1 makes in the side such as film elongation or thermal conductivity Still there is room for improvement in face.

The present invention is to complete in view of the foregoing, its problem is, there is provided can form film elongation and thermal conductivity The aromatic polyester of excellent film, aromatic polyester liquid composition comprising above-mentioned aromatic polyester, aromatic polyester film Manufacture method and aromatic polyester film.

Solutions to solve the problem

The 1st pattern of the present invention is a kind of aromatic polyester, as Component units, it includes：(A) following formula (a) institute table Repetitive unit, the repetitive unit in (B) aromatic dicarboxylic acid source, (C) shown is selected from aromatic diamine and the fragrance with hydroxyl The repetitive unit in the aromatic amine source in race's amine and the repetitive unit in (D) aromatic diol source, relative to (A) to (D) Repetitive unit it is total, the containing ratio of the repetitive unit of (A) is 10 moles of % less than 20 moles of %, the repetition list of (B) The containing ratio of member is more than 40 moles of % and is 45 moles of below %, and the repetitive unit of (C) and the total of repetitive unit of (D) are contained Rate is more than 40 moles of % and is 45 moles of below %, and the containing ratio of the repetitive unit of (D) rubs more than 0 mole of % and less than 15 You are %.

-O-Ar¹-CO-(a)

(in formula, Ar¹Represent 1,4- phenylenes, 2,6- naphthylenes or 4,4 '-biphenylene；Ar¹In represented group At least one hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl.)

The 2nd pattern of the present invention is a kind of aromatic polyester liquid composition, it contains the 1st pattern of the invention described above Aromatic polyester and non-protonic solvent.

The 3rd pattern of the present invention is a kind of manufacture method of aromatic polyester film, it includes：By the 2nd of the invention described above the The aromatic polyester liquid composition of pattern is coated on the process on supporting substrates and from the above-mentioned fragrance on above-mentioned supporting substrates The process that solvent is removed in adoption ester liquid composition.

The 4th pattern of the present invention is a kind of aromatic polyester film, and it includes the fragrant adoption of the 1st pattern of the invention described above Ester.

That is, the present invention includes following pattern.

[1] a kind of aromatic polyester, as Component units, it includes：

(A) repetitive unit represented by following formula (a),

(B) repetitive unit in aromatic dicarboxylic acid source,

(C) selected from aromatic diamine and with hydroxyl aromatic amine in aromatic amine source repetitive unit and

(D) repetitive unit in aromatic diol source；

Relative to (A) to (D) repetitive unit it is total,

(A) containing ratio of repetitive unit is 10 moles of % less than 20 moles of %,

(B) containing ratio of repetitive unit is more than 40 moles of % and is 45 moles of below %,

(C) repetitive unit and total containing ratio of the repetitive unit of (D) more than 40 moles of % and is 45 moles of below %,

(D) containing ratio of repetitive unit is more than 0 mole of % and is less than 15 moles of %.

-O-Ar¹-CO- (a)

[2] aromatic polyester according to [1], wherein, in above-mentioned formula (a), Ar¹For 1,4- phenylenes or 2,6- Asias naphthalene Base.

[3] aromatic polyester according to [1] or [2], wherein, the repetitive unit of above-mentioned (B) is following formula (b) institute table The repetitive unit shown.

-CO-Ar²-CO- (b)

(in formula, Ar²Represent 1,4- phenylenes, 1,3- phenylenes, 2,6- naphthylenes or diphenyl ether -4,4 '-diyl；Ar²Institute At least one hydrogen atom in the group of expression is optionally separately substituted by halogen atom, alkyl or aryl.)

[4] aromatic polyester according to [3], wherein, in above-mentioned formula (b), Ar²For 1,4- phenylenes, 1,3- Asias benzene Base or 2,6- naphthylenes.

[5] aromatic polyester according to any one of [1] to [4], wherein, the repetitive unit of above-mentioned (C) is following Repetitive unit represented by formula (c).

-X-Ar³-NH- (c)

(in formula, Ar³Represent 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes；Ar³In represented group at least One hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl；X expression-O- or-NH-.)

[6] aromatic polyester according to [5], wherein, in above-mentioned formula (c), Ar³For unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes.

[7] aromatic polyester according to any one of [1] to [6], wherein, the repetitive unit of above-mentioned (D) is following Repetitive unit represented by formula (d).

-O-Ar⁴-O- (d)

(Ar⁴Represent 1,4- phenylenes, 1,3- phenylenes or 4,4 '-biphenylene；Ar⁴At least one in represented group A hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl.)

[8] aromatic polyester according to [7], wherein, in above-mentioned formula (d), Ar⁴For unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 4,4 '-biphenylene.

[9] a kind of aromatic polyester film, it includes the aromatic polyester any one of [1] to [8].

[10] a kind of aromatic polyester liquid composition, its contain aromatic polyester any one of [1] to [8] and Non-protonic solvent.

[11] the aromatic polyester liquid composition according to [10], wherein, relative to 100 mass of non-protonic solvent Part, containing more than 0.01 mass parts and 100 aromatic polyesters below mass part.

[12] the aromatic polyester liquid composition according to [10] or [11], wherein, above-mentioned non-protonic solvent is It is halogen-free the non-protonic solvent of atom.

[13] the aromatic polyester liquid composition according to any one of [10] to [12], wherein, it is above-mentioned non-proton Property solvent dipole moment be more than 3 and less than 5.

[14] a kind of manufacture method of aromatic polyester film, it includes：

Make process that the aromatic polyester liquid composition any one of [10] to [13] is cast on supporting substrates, With

The process that solvent is removed from the above-mentioned aromatic polyester liquid composition on above-mentioned supporting substrates.

The effect of invention

According to the present invention, it is possible to provide the aromatic polyester of film elongation and the excellent film of thermal conductivity can be formed, used The aromatic polyester liquid composition of above-mentioned aromatic polyester, the manufacture method of aromatic polyester film and aromatic polyester film.

Brief description of the drawings

Fig. 1 is the stereogram for the aromatic polyester for being denoted as an embodiment of the invention.

Embodiment

＜ aromatic polyesters ＞

The aromatic polyester of the 1st pattern of the present invention can suitably be used as the membrane material of electric substrate etc..

As in the aromatic polyester of an embodiment of the invention, as Component units, it includes：

(A) repetitive unit represented by following formula (a) (hereinafter also referred to as repetitive unit (A) or the repetitive unit of (A)),

(B) repetitive unit (hereinafter also referred to as repetitive unit (B) or the repetitive unit of (B)) in aromatic dicarboxylic acid source,

(C) the aromatic amine source in the aromatic amine selected from aromatic diamine and with hydroxyl repetitive unit (it is following, The also referred to as repetitive unit of repetitive unit (C) or (C)) and

(D) repetitive unit (hereinafter also referred to as repetitive unit (D) or the repetitive unit of (D)) in aromatic diol source,

Relative to (A) to (D) repetitive unit it is total,

-O-Ar¹-CO- (a)

It should be noted that in above-mentioned aromatic polyester, the total of the repetitive unit of (A) to (D) rubs no more than 100 You are %.

In the present specification, " source " represents：Due to being polymerize, chemical constitution changes.

(repetitive unit (A))

Repetitive unit (A) is represented with following formula (a).

-O-Ar¹-CO- (a)

Ar in formula (a)¹Preferably 1,4- phenylenes, 2,6- naphthylenes or 4,4 '-biphenylene.As Ar¹, more preferably For 1,4- phenylenes or 2,6- naphthylenes.

As repetitive unit (A), such as the repetitive unit in P-hydroxybenzoic acid source, 2- hydroxyl -6- naphthoic acids can be enumerated The repetitive unit in source, the repetitive unit in 4- hydroxyls -4 '-biphenyl carboxylic acids source etc..Wherein, preferred P-hydroxybenzoic acid source Repetitive unit or the repetitive unit in 2- hydroxyl -6- naphthoic acids source.

(repetitive unit (B))

Repetitive unit (B) is the repetitive unit in aromatic dicarboxylic acid source.

As repetitive unit (B), such as can enumerate：From from terephthalic acid (TPA), M-phthalic acid, diphenyl ether -2,2 ' - Dicarboxylic acids, diphenyl ether -2,3 '-dicarboxylic acids, diphenyl ether -2,4 '-dicarboxylic acids, diphenyl ether -3,3 '-dicarboxylic acids, diphenyl ether -3,4 ' - Dicarboxylic acids, diphenyl ether -4,4 '-dicarboxylic acids, phthalic acid, 2,6 naphthalene dicarboxylic acid, diphenic acid and double (to carboxyl phenyl) alkane The repetitive unit of at least one aromatic dicarboxylic acid of middle selection.Wherein, from the viewpoint of widely using property height, preferably always At least one repetitive unit for coming from the repetitive unit of terephthalic acid (TPA) and being selected in the repetitive unit of M-phthalic acid, More preferably derive from the repetitive unit of M-phthalic acid.

Repetitive unit (B) is preferably the repetitive unit represented by following formula (b).

-CO-Ar²-CO- (b)

Ar in formula (b)²Preferably 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes.

As repetitive unit (B), preferably Ar²For Isosorbide-5-Nitrae-phenylene repetitive unit (that is, from the weight of terephthalic acid (TPA) Multiple unit), Ar²For repetitive unit (that is, from the repetitive unit of M-phthalic acid), the Ar of 1,3- phenylenes²For 2,6- Asias naphthalene The repetitive unit (that is, from the repetitive unit of 2,6- naphthalene dicarboxylic acids) and Ar of base²For the repetition list of diphenyl ether -4,4 '-diyl First (that is, from diphenyl ether -4, the repetitive unit of 4 '-dicarboxylic acids).

(repetitive unit (C))

Repetitive unit (C) is the repetition in the aromatic amine source in the aromatic amine selected from aromatic diamine and with hydroxyl Unit.Repetitive unit (C) is preferably the repetitive unit represented by following formula (c).

-X-Ar³-NH-(c)

(in formula, Ar³Represent 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes；Ar³In represented group at least One hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl, X expression-O- or-NH-.)

Ar in formula (c)³Preferably unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes.

As repetitive unit (C), such as the repetitive unit in 3- amino-phenols source, the weight in 4-aminophenol source can be enumerated Multiple unit, the repetitive unit in 1,4- phenylenediamines source, the repetitive unit etc. in 1,3- phenylenediamines source.Wherein, preferably The repetitive unit in 4-aminophenol source.

Above-mentioned Ar¹、Ar²And Ar³At least one hydrogen atom in represented group is optionally separately former by halogen Son, alkyl or aryl substitution.

As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms and iodine atom can be enumerated.

As the alkyl of abovementioned alkyl, preferably carbon number 1~10, such as methyl, ethyl, n-propyl, isopropyl, just can be enumerated Butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, 2- ethylhexyls, n-octyl, n-nonyl and the positive last of the ten Heavenly stems Base.

As the aryl of above-mentioned aryl, preferably carbon number 6~20, such as phenyl, o-tolyl, a tolyl, right can be enumerated Tolyl, 1- naphthyls and 2- naphthyls.

In above-mentioned Ar¹、Ar²And Ar³In the case that the hydrogen atom of represented group is substituted by these groups, on its number Amount, on each single group, separately preferably less than 2, more preferably 1.

(repetitive unit (D))

Repetitive unit (D) is the repetitive unit in aromatic diol source.

As repetitive unit (D), such as the repetitive unit represented by following formula (d) can be enumerated.

-O-Ar⁴-O- (d)

Ar in formula (d)⁴Preferably unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 4,4 '-biphenylene.

Ar in the formula (d)⁴At least one hydrogen atom in represented group optionally separately by halogen atom, Alkyl or aryl substitutes.

As above-mentioned substituent, can enumerate：With as above-mentioned Ar¹、Ar²And Ar³The substituent that can have and the halogen illustrated The same group of atom, alkyl or aryl.

As repetitive unit (D), specifically, the repetitive unit in hydroquinone source, resorcinol source can be enumerated Repetitive unit, the repetitive unit etc. in 4,4 '-xenol source.Wherein, the preferred repetitive unit in hydroquinone source.

Aromatic polyester as an embodiment of the invention is characterized in that it includes above-mentioned (A) to (D) Repetitive unit, and its composition rubs relative to the total of the repetitive unit of (A)~(D), the containing ratio of the repetitive unit of (A) for 10 Your % is less than 20 moles of %, and the containing ratio of the repetitive unit of (B) is more than 40 moles of % and is 45 moles of below %, (C) Repetitive unit and total containing ratio of repetitive unit of (D) more than 40 moles of % and be 45 moles of below %, the repetition list of (D) The containing ratio of member more than 0 mole of % and is less than 15 moles of %.

(A) containing ratio of repetitive unit is preferably 16 moles of more than % relative to the total of the repetitive unit of (A)~(D) And 19 moles of below %, more preferably 16 moles of more than % and 18 mole of below %.

(B) containing ratio of repetitive unit relative to the repetitive unit of (A)~(D) it is total preferably greater than 40 moles of % and For 43 moles of below %, more preferably 41 moles of more than % and 42 mole of below %.

(C) containing ratio of repetitive unit relative to the repetitive unit of (A)~(D) it is total preferably greater than 25 moles of % and For 40 moles of below %, more preferably above 28 moles of % and be 35 moles of below %, more preferably 29 moles of more than % and 32 moles of below %.

(D) containing ratio of repetitive unit relative to the repetitive unit of (A)~(D) it is total be preferably 0.5 mole of % with Above and it is less than 15 moles of %, is more preferably 10 moles of more than % and 12 mole of below %.

(C) repetitive unit and total containing ratio of the repetitive unit of (D) relative to the repetitive unit of (A)~(D) conjunction Meter is preferably greater than 40 moles of % and is 43 moles of below %, more preferably 41 moles of more than % and 42 mole of below %.

In the present invention, if the containing ratio of repetitive unit (A) 10 rubs relative to adding up to for the repetitive unit of (A) to (D) You are more than %, then steeply rising for viscosity when can inhibit manufacture, is preferable from the viewpoint of manufacture view therefore.Separately Outside, if the containing ratio of repetitive unit (A) is less than 20 moles of % relative to the total of the repetitive unit of (A) to (D), to non-proton The dissolubility of property solvent becomes good.

In addition, by making the containing ratio of repetitive unit (A) add up to above-mentioned rule relative to the repetitive unit of (A) to (D) Fixed scope, can make the film elongation of the aromatic polyester film of the aromatic polyester comprising the present invention become larger.Therefore, comprising this The aromatic polyester film of the aromatic polyester of invention will not be cracked when carrying out flexing processing (bending machining), or can be with Largely suppress the generation of crackle.

In addition, by making containing ratio the adding up to relative to the repetitive unit of (A) to (D) of repetitive unit (A) Defined scope is stated, can become higher the thermal conductivity of the aromatic polyester film of the aromatic polyester comprising the present invention.

In the present invention, by making containing ratio the adding up to relative to the repetitive unit of (A) to (D) of repetitive unit (B) Scope as defined in above-mentioned, can help to give play to the flexibility of the aromatic polyester film of the aromatic polyester comprising the present invention, can So that the film elongation of above-mentioned film becomes larger.Therefore, the aromatic polyester film of the aromatic polyester comprising the present invention is carrying out flexing It will not be cracked when processing (bending machining), or can largely suppress the generation of crackle.

In the present invention, total containing of the containing ratio of repetitive unit (B) preferably with repetitive unit (C) and repetitive unit (D) There is the rate substantially the same.It is " substantially the same " to represent：The containing ratio of repetitive unit (B) is relative to repetitive unit (C) and repeats single Within total containing ratio of first (D) is ± 1 mole of %.

The containing ratio of repetitive unit (B) relative to total containing ratio of repetitive unit (C) and repetitive unit (D) can be- 10 moles of %~+10 mole %.Usage rate by making corresponding monomer changes within the range, so that fragrance can also be controlled The degree of polymerization of adoption ester.

Repetitive unit (D) uses preferably in the form of replacing a part of repetitive unit (C), in this case Replacement amount, in general, being scaled molar ratio (D)/(C) (that is, the repetitive units (D) relative to the repetitive unit (C) used originally Content/used originally repetitive unit (C) amount) when, be more than 0.01 and less than 0.75, be preferably more than 0.02 and 0.65 Below.

In the present invention, the containing ratio of repetitive unit (D) relative to (A) to (D) if repetitive unit total containing ratio More than 0 mole %, then viscosity when can suppress manufacture steeply rise, therefore, from manufacture it is upper from the viewpoint of be it is preferable, Furthermore it is possible to the film elongation of the aromatic polyester film of the aromatic polyester comprising the present invention is set to become larger.Therefore, comprising the present invention The aromatic polyester film of aromatic polyester will not be cracked when carrying out flexing processing (bending machining), or can be larger Suppress to degree the generation of crackle.In addition, by making the containing ratio of repetitive unit (D) relative to the repetitive unit of (A) to (D) Add up in above-mentioned prescribed limit, can become higher the thermal conductivity of the aromatic polyester film of the aromatic polyester comprising the present invention.

The aromatic polyester of the present invention includes repetitive unit as described above, as its manufacture method, can use with Each corresponding monomer of repetitive unit, i.e., aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic amine, aromatic diol etc. or Person is selected from least one of their ester formative derivative and acid amides formative derivative derivative, and according to common side Method, method such as described in Japanese Unexamined Patent Publication 2002-220444, Japanese Unexamined Patent Publication 2002-146003 etc. manufacture.

In addition, the use mole % of each monomer is identical with mole % shown in above-mentioned repetitive unit.

Here, ester formative derivative and acid amides as the carboxylic acid in aromatic dicarboxylic acid, aromatic hydroxy-carboxylic etc. Formative derivative, such as can enumerate：Carboxylic acid structure is transformed to the reactivities such as carboxylic acid halides structure, acid anhydride structure height and promotes life The derivative of the structure of reaction into ester, acid amides etc. etc；Carboxylic acid structure is transformed to the ester knot with the formation such as alcohols, ethylene glycol The derivative of structure, it is to generate ester by ester exchange reaction or the derivative of acid amides etc is generated by acid amides exchange reaction.

In addition, as the phenol hydroxyl in aromatic diol, aromatic hydroxy-carboxylic, aromatic amine (such as amino-phenol) etc. The ester formative derivative of base, can enumerate for example：Phenolic hydroxyl group is transformed to the ester structure formed with the carboxylic acids of carbon number 1~5 Derivative, it is the derivative that ester etc is generated by ester exchange reaction.

Acid amides as the amino in the aromatic amines such as aromatic diamine, amino-phenol forms derivative, can enumerate for example： Amino is transformed to the derivative of the acid amides formed with the carboxylic acids of carbon number 1~5, it is to generate acid amides by acid amides exchange reaction Etc derivative.

As the representative preparation method of the aromatic polyester of the present invention, such as can enumerate：By aromatic hydroxy-carboxylic, aminobenzene The phenolic hydroxyl group of phenol, aromatic diamine, aromatic diol etc., amino are acylated using the fatty acid anhydride of excess quantity and obtain acyl Compound, which carries out ester exchange with the carboxyl of aromatic dicarboxylic acid, aromatic hydroxy-carboxylic etc. or acid amides is exchanged and Melt polymerization method of polycondensation etc..

Here, in acylation reaction, relative to the total of phenolic hydroxyl group and amino, the additive amount of fatty acid anhydride is usually 1.0~1.2 times of equivalents, are preferably 1.05~1.1 times of equivalents.If the additive amount of fatty acid anhydride is less than 1.0 times of equivalents, during polycondensation Acylate, starting monomer etc. distil, and have reaction system to hold susceptible to plugging tendency, in addition, when more than 1.2 times of equivalents, there is gained The tendency that aromatic polyester colours.That is, if the additive amount of fatty acid anhydride is in above range, can suppress in polycondensation The distillation of acylate, starting monomer etc., reaction system becomes to be not susceptible to block, in addition, gained aromatic polyester becomes to be not easy Colour.

Acylation reaction carried out usually at 130~180 DEG C 5 minutes~10 it is small when, but preferably carried out at 140~160 DEG C 10 minutes~3 it is small when.

The fatty acid anhydride used in acylation reaction is not particularly limited, for example, can enumerate acetic anhydride, propionic andydride, butyric anhydride, Isobutyric anhydride, valeric anhydride, neopentanoic acid acid anhydride, 2 ethyl hexanoic acid acid anhydride, monochloracetic acid acid anhydride, dichloro- acetic anhydride, trichloroacetic acid acid anhydride, Monobromo-acetic acid acid anhydride, two bromo acetic anhydrides, three bromo acetic anhydrides, monofluoro-acetic acid acid anhydride, two fluoro acetic anhydrides, trifluoroacetic acid Acid anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, bromo-propionic acid acid anhydride etc., they can be used one kind or two or more.From price and from From the viewpoint of rationality, at least one of acetic anhydride, propionic andydride, butyric anhydride and isobutyric anhydride are preferably selected from, more preferably Acetic anhydride.

In ester exchange and acid amides exchange, preferably to become 0.8~1.2 times of equivalent relative to the total amount of acyl group and amide groups Mode adjust carboxyl.

Additionally, it is preferred that 130~400 DEG C below with 0.1~50 DEG C/min of ratio carry out heating side carry out ester exchange and Acid amides exchanges, and more preferably carrying out heating side below with 0.3~5 DEG C/min of ratio at 150~350 DEG C carries out ester exchange and acyl Amine exchanges.At this time, in order to make balanced sequence, preferably make aliphatic acid and the evaporation of unreacted fatty acid anhydride of by-product etc. and distill and remove Go to outside system.

It can be carried out in the presence of a catalyst it should be noted that acylation reaction, ester exchange and acid amides exchange.

As catalyst, the known catalyst as the catalyst for polymerization of polyester all the time can be used, such as It can enumerate：The metal salt catalysts such as magnesium acetate, stannous acetate, butyl titanate, lead acetate, sodium acetate, potassium acetate, three acidifying antimony Agent；Organic compound catalysts such as N, N- dimethyl aminopyridine, N- methylimidazoles etc..

Among these catalyst, preferably using N, it is former that N- dimethyl aminopyridines, N- methylimidazoles etc. include more than 2 nitrogen The miscellaneous cyclic compound of son (with reference to Japanese Unexamined Patent Publication 2002-146003).

The polycondensation exchanged based on ester exchange, acid amides is usually carried out using melt polymerization, but and can also use melt polymerization And solid phase.On solid phase, preferably by extracting polymer out from melt polymerization process, afterwards by above-mentioned polymer powder It is broken and powdered or sheet is made, then carried out using known method for solid phase polymerization.Specifically, such as can enumerate： Under the inert atmospheres such as nitrogen, at 180~350 DEG C, with the heat-treating methods of solid state shape progress 1~30 when small etc.. Solid phase can carry out while stirring, can not also stir and be carried out with static condition.It should be noted that it can also pass through Possess appropriate rabbling mechanism and melt polymerization groove and solid phase groove is become same reactive tank., can after solid phase With using known method (for example, the resin harness made of twin-screw mixer extruder cut by comminutor Method) gained aromatic polyester is granulated, it is formed.

As the manufacture device of aromatic polyester, any one of batch equipment, continuous apparatus can be used.

In this way, the aromatic polyester of the manufacture present invention, but in aromatic polyester, the object of the invention can also not damaged In the range of coordinate known to filler, additive etc..

As filler, such as can enumerate：Epoxy powder, melamine resin powder, carbamide resin powder, benzoguanamine resin The organic system filler such as powder, styrene resin；Silica, aluminium oxide, titanium oxide, zirconium oxide, kaolin, calcium carbonate, carbonization Inorganic fillers such as silicon, calcium phosphate, boron nitride etc..

As additive, known coupling agent, antisettling agent, ultra-violet absorber, heat stabilizer etc. can be enumerated.

In addition, in aromatic polyester, within the scope without prejudice to the object of the present invention, can also by polypropylene, polyamide, Polyester, polyphenylene sulfide, polyether-ketone, makrolon, polyether sulfone, polyphenylene oxide and its modifier；The thermoplastic resins such as polyetherimide； Elastomers such as the copolymer of glycidyl methacrylate and polyethylene etc. coordinate one or more kinds of.

In the case of being combined with these fillers in the aromatic polyester of the present invention, aromatic polyester is being set to 100 matter When measuring part, the content of above-mentioned filler is preferably more than 0 mass parts and is 100 below mass part.

＜ aromatic polyester liquid compositions ＞

The aromatic polyester liquid composition of the 2nd pattern of the present invention is to contain aromatic polyester as described above and non-matter The liquid composition of sub- property solvent, can be manufactured by the way that both are mixed.

In aromatic polyester liquid composition, when the content of aprotic liquids is set to 100 mass parts, preferred fragrance The content of adoption ester is more than 0.01 mass parts and 100 is below mass part.If the content of aromatic polyester is less than 0.01 mass parts, Then the solution viscosity of above-mentioned liquid composition is too low and have the tendency that can not be uniformly coated, if more than 100 mass parts, have on State the tendency that high viscosity occurs for liquid composition.That is, if the content of aromatic polyester is above-mentioned liquid group in above range The solution viscosity of compound will not become too low and can be uniformly coated, it is additionally possible to suppress the height of above-mentioned liquid composition glues Degreeization.

From the viewpoint of workability, economy, when the content of aprotic liquids is set to 100 mass parts, fragrance The content of adoption ester is more preferably more than 1 mass parts and 50 is below mass part, more preferably more than 2 mass parts and 40 mass Below part.

The viscosity of above-mentioned liquid composition is preferably more than 500cP and below 10000CP.

As non-protonic solvent, such as can enumerate：1-chlorobutane, chlorobenzene, 1,1- dichloroethanes, 1,2- dichloroethanes, The halogen-based solvents such as chloroform, 1,1,2,2- tetrachloroethanes；The ether series solvents such as Anaesthetie Ether, tetrahydrofuran, 1,4- dioxanes；Third The ketone series solvents such as ketone, cyclohexanone；The ester series solvents such as ethyl acetate；Ester series solvent in gamma-butyrolacton etc.；Ethylene carbonate, carbonic acid The carbonate-based solvents such as propylene；The amine series solvents such as triethylamine, pyridine；The nitrile series solvents such as acetonitrile, succinonitrile；N, N '-diformazan The acid amides series solvent such as base formamide, N, N '-dimethyl acetamide, tetramethylurea, 1-methyl-2-pyrrolidinone；Nitromethane, nitro The nitro series solvent such as benzene；The thioether series solvent such as dimethyl sulfoxide (DMSO), sulfolane；The phosphorus such as hexamethyl-phosphoramide, TRI N BUTYL PHOSPHATE Sour series solvent etc..

Among these, from the aspect that environment influences preferably using being halogen-free the solvent of atom, in addition, from dissolving Property from the viewpoint of and preferably using dipole moment be more than 3 and less than 5 solvent.

As the compound for belonging to aprotic compound and dipole moment is 3~5, dimethyl sulfoxide (DMSO) (dipole can be exemplified Square：4.1 debye), DMAC N,N' dimethyl acetamide (dipole moment：3.7 debye), N,N-dimethylformamide (3.9 debye), N- methyl Pyrrolidones (dipole moment：4.1 debye).

" dipole moment " is that the absolute value of the positive and negative charge produced on each atom is with being bonded distance in interatomic bonding Product, with vector representation.

Here, in the present specification, " liquid composition " refers to：The combination of liquid condition is shown as at 20~40 DEG C Thing.

In liquid composition, aromatic polyester is not necessarily required whole amount and all dissolves, but more few more excellent without the amount of dissolving Choosing (such as without dissolve amount be preferably less than 0.5%), more preferably whole amount all dissolves.

The manufacture method ＞ of ＜ aromatic polyester films

The manufacture method of the aromatic polyester film of the 3rd pattern as the present invention is illustrated.

The manufacture method of the aromatic polyester film of the present invention includes：Above-mentioned such aromatic polyester liquid composition is set to exist The process being cast on supporting substrates；With the removing solvent from the above-mentioned aromatic polyester liquid composition on above-mentioned supporting substrates Process.

Above-mentioned manufacture method can also include the process for removing above-mentioned supporting substrates after the process of above-mentioned removing solvent.

As above-mentioned supporting substrates, preferably polyethylene terephthalate (PET) film, polyimide film, glass plate or Metal foil.

In the present invention, as needed, filter aromatic polyester liquid composition by using filter etc. and remove Trickle foreign matter contained in aromatic polyester liquid composition is stated, then, for example, by rolling method, dip coating, spraying process, spin coating The various means such as method, curtain coating, slot coated method, silk screen print method, surface is flat and is equably cast on supporting substrate.

The removing method of non-protonic solvent is not particularly limited, and the method for preferably making evaporation of the solvent and being removed can To illustrate：Solvent is steamed separately through any one of heating, decompression and ventilation, or by the two or more combinations in them The method of hair.Wherein, from the viewpoint of production efficiency and treatability, preferably heated and make the method for evaporation of the solvent, more It is preferred that make the method for evaporation of the solvent when divulging information and heating.

Heating at this time carried out preferably at 60~200 DEG C 10 minutes~2 it is small when, next, in order to carry out fragrance in the lump The further molecular weight of adoption ester, when heating 30 minutes~5 is small preferably at 200~400 DEG C.It should be noted that Here, " removing solvent " may not represent " removing the solvent of whole amount ", such as solvent is preferably fully removed, until fragrant adoption Untill obvious weight change does not occur for ester film.Here, " obvious weight change " refers to：When being placed 30 minutes at 100 DEG C, Weight is reduced to less than 0.1%.

＜ aromatic polyester films ＞

The aromatic polyester film of the 4th pattern of the present invention includes the fragrant adoption as an embodiment of the invention Ester, such as can be manufactured by above-mentioned manufacture method.On the thickness of the aromatic polyester film of the present invention, from film Property, be preferably 0.5~500 μm from the viewpoint of mechanical property, from the viewpoint of treatability, more preferably 1~200 μm.

It should be noted that " thickness " mentioned here is equally spaced to measure arbitrary 5~10 by micrometer counter device The average value being worth obtained from a position.

On the aromatic polyester film of the present invention, thermal conductivity and stretching are being measured by the method described in aftermentioned embodiment During elongation at break, preferably thermal conductivity is more than 0.28W/ (mK) and tension fracture elongation rate is more than 20.0%.

In addition, the aromatic polyester film on the present invention, not only thermal conductivity is good, film elongation is big etc. excellent, And show the excellent characteristic such as high frequency characteristics, agent of low hygroscopicity, therefore, available for receiving much concern in recent years based on lamination work The semiconductor package body of skill etc. or the multilayer printed board of motherboard, flexible printed circuit board, tape automated bonding film, other The base material of eight-millimeter videotape, the base material of business digital video tape, the base material, the base of polarizing coating of transparent conductivity (ITO) film Material, it is various cook food with, the packaging film of microwave stove heat, electromagnetic shielding material be with film, antibiotic property film, gas separation film Deng.

＜ metallic substrates circuit substrates ＞

The metallic substrates circuit substrate of aromatic polyester film to having used the present invention illustrates.

Use the metallic substrates circuit substrate of the aromatic polyester film of the present invention except using above-mentioned aromatic polyester film Beyond insulating layer, the composition same with known metallic substrates circuit substrate can be formed, same method can be passed through To manufacture.

Metallic substrates circuit substrate can for example manufacture in the following way：What is be made of a piece of above-mentioned aromatic polyester film The one or both sides for the insulating layer that insulating layer or the stacking above-mentioned aromatic polyester film of multi-disc form are equipped with metal layer and make layer Stack, forms defined circuit pattern to the metal layer of the layered product by etching etc., keeps formed with the circuit pattern Layered product and complete to manufacture, or as needed stacking two panels more than formation have the layered product of the circuit pattern and complete to make Make.Metallic substrates circuit substrate is preferably to be laminated with the substrate of metal layer on the two sides of aromatic polyester film.

In the case where being laminated with the insulating layer of the above-mentioned aromatic polyester film of multi-disc, these multi-disc aromatic polyester films can be with It is all identical, can also only part it is identical, can also be all different.In addition, as long as its piece number does not limit especially then for more than 2 System, such as preferably more than 2 and less than 10.Such insulation layers can such as make as follows：By multi-disc aromatic polyester Film is overlapping in the thickness direction thereof, carries out heating compacting and makes its fused with one another, so that it is integrated.

The material of metal layer is preferably copper, aluminium, silver or comprising the alloy selected from least one of they metal.Wherein, From the viewpoint of with more superior electrical conductivity, preferably copper or copper alloy.Moreover, be easily processed, can be simply forming from material, From the viewpoint of economy is also excellent, metal layer is preferably the layer being made of metal foil, the layer being more preferably made of copper foil. In the case of the two sides that metal layer is arranged to insulating layer, the material of these metal layers may be the same or different.

As the method for setting metal layer, may be exemplified：The method for making metal foil be fused to surface of insulating layer；Use bonding agent The method for making metal foil be adhered to surface of insulating layer；Pass through plating, silk screen print method or sputtering method metal powder or clipped wire The method of son covering surface of insulating layer.

It is in the case that the stacking above-mentioned aromatic polyester film of multi-disc forms, by by these aromatic polyester films in insulating layer Overlap in the thickness direction thereof, it is further overlapping on the surface of one or two aromatic polyester film on the outermost side These metal foils and multi-disc aromatic polyester film are carried out heating compacting by metal foil, so that when forming insulating layer, can be exhausted The one or two sides of edge layer sets metal layer at the same time.

On another scheme of the aromatic polyester of the present invention, following aromatic polyester can be enumerated,

As Component units, it includes：

(A) repetitive unit, the repetitive unit and 4- in 2- hydroxyl -6- naphthoic acids source in P-hydroxybenzoic acid source are selected from At least one of the repetitive unit in hydroxyl -4 '-biphenyl carboxylic acids source repetitive unit,

It is preferably selected from the repetitive unit in P-hydroxybenzoic acid source and the repetitive unit in 2- hydroxyl -6- naphthoic acids source At least one of repetitive unit,

The more preferably repetitive unit in 4-HBA source；

(B) derive from from terephthalic acid (TPA), M-phthalic acid, diphenyl ether -2,2 '-dicarboxylic acids, diphenyl ether -2,3 '-dicarboxyl Acid, diphenyl ether -2,4 '-dicarboxylic acids, diphenyl ether -3,3 '-dicarboxylic acids, diphenyl ether -3,4 '-dicarboxylic acids, diphenyl ether -4,4 '-dicarboxyl At least one aromatic series two selected in acid, phthalic acid, 2,6 naphthalene dicarboxylic acid, diphenic acid and double (to carboxyl phenyl) alkane The repetitive unit of carboxylic acid,

It is preferably selected from the repetitive unit in terephthalic acid (TPA) source and the repetitive unit in M-phthalic acid source at least A kind of repetitive unit,

The more preferably repetitive unit in M-phthalic acid source；

(C) selected from the repetitive unit in 3- amino-phenols source, the repetitive unit in 4-aminophenol source, 1,4- phenylenes two At least one of the repetitive unit in amine source and the repetitive unit in 1,3- phenylenediamine source repetitive unit,

The preferably repetitive unit in 4-aminophenol source,

The more preferably repetitive unit in 4- hydroxyacetanilides source；With

(D) repetitive unit selected from hydroquinone source, the repetitive unit in resorcinol source and 4,4 '-xenol come At least one of the repetitive unit in source repetitive unit,

The preferably repetitive unit in hydroquinone source；

Relative to (A) to (D) repetitive unit it is total,

Preferably 16 moles of more than % and 19 mole of below %,

More preferably 16 moles of more than % and 18 mole of below %；

Preferably greater than 40 moles of % and be 43 moles of below %,

More preferably 41 moles of more than % and 42 mole of below %；

Preferably 41 moles of more than % and 42 mole of below %；

(D) containing ratio of repetitive unit is more than 0 mole of % and is less than 15 moles of %,

Preferably 0.5 mole of % less than 15 moles of %,

More preferably 10 moles of more than % and 12 mole of below %；

(C) containing ratio of repetitive unit is preferably greater than 25 moles of % and is 40 moles of below %,

More preferably above 28 moles of % and be 35 moles of below %,

More preferably 29 moles of more than % and 32 mole of below %.

Embodiment

Hereinafter, the present invention is further illustrated by embodiment, but the present invention is not limited to following embodiment.

The manufacture ＞ of ＜ aromatic polyesters

《Embodiment 1》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, 4- is added Hydroxybenzoic acid (hereinafter referred to as POB) 248.6g (1.8 moles), 4- hydroxyacetanilides (hereinafter referred to as APAP) 468.6g (3.1 moles), M-phthalic acid (hereinafter referred to as IPA) 681.1g (4.1 moles), hydroquinone (hereinafter referred to as HQ) 110.1g (1.0 moles) and acetic anhydride 806.5g (7.90 moles).Will be in reactor fully with nitrogen into after line replacement, in nitrogen 150 DEG C were warming up to 15 minutes under gas air-flow, keeps temperature, when making its reflux 3 small.

Afterwards, use be warming up to 300 within 300 minutes when the by-product distillated acetic acid and unreacted acetic anhydride are distilled off DEG C, it will confirm that the time point of moment of torsion rising is considered as reaction and terminates, take out content.Next room temperature is cooled to, with thick After pulverizer is crushed, in a nitrogen atmosphere with 290 DEG C keep 3 it is small when, with solid phase carry out polymerisation and obtain aromatic series Polyester powder.

《Embodiment 2》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 221.0g (1.6 moles), APAP 483.7g (3.2 moles), IPA697.7g (4.2 moles), HQ 110.1g (1.0 moles) and Acetic anhydride 796.3g (7.80 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 minutes under stream of nitrogen gas 150 DEG C are warming up to, keeps temperature, when making its reflux 3 small.

《Embodiment 3》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 248.6g (1.8 moles), APAP 438.4g (2.9 moles), IPA 681.1g (4.1 moles), HQ 132.1g (1.2 moles) and Acetic anhydride 826.9g (8.10 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 minutes under stream of nitrogen gas 150 DEG C are warming up to, keeps temperature, when making its reflux 3 small.

《Embodiment 4》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 221.0g (1.6 moles), APAP 453.5g (3.0 moles), IPA697.7g (4.2 moles), HQ 132.1g (1.2 moles) and Acetic anhydride 816.7g (8.00 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 minutes under stream of nitrogen gas 150 DEG C are warming up to, keeps temperature, when making its reflux 3 small.

《Embodiment 5》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 234.8g (1.7 moles), APAP 476.2g (3.15 moles), IPA 689.4g (4.15 moles), HQ 110.1g (1.0 moles) And acetic anhydride 801.4g (7.85 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 points under stream of nitrogen gas Clock is warming up to 150 DEG C, keeps temperature, when making its reflux 3 small.

《Production Example 1》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, 2- is added Hydroxyl -6- naphthoic acids (hereinafter referred to as HNA) 376.4g (2.0 moles), APAP 604.6g (4.0 moles), IPA 664.5g (4.0 moles) and acetic anhydride 714.6g (7.00 moles).Will be in reactor fully with nitrogen into after line replacement, in stream of nitrogen gas It is lower to be warming up to 150 DEG C with 15 minutes, temperature is kept, when making its reflux 3 small.

《Production Example 2》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, HNA is added 282.3g (1.5 moles), APAP 642.4g (4.25 moles), IPA 706.1g (4.25 moles) and acetic anhydride 689.1g (6.75 Mole).In reactor fully with nitrogen into after line replacement, 150 DEG C will be warming up to 15 minutes under stream of nitrogen gas, keeps warm Degree, when making its reflux 3 small.

《Production Example 3》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 276.2g (2.0 moles), APAP 377.9g (2.5 moles), IPA 664.5g (4.0 moles), HQ 165.2g (1.5 moles) and Acetic anhydride 867.8g (8.50 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 minutes under stream of nitrogen gas 150 DEG C are warming up to, keeps temperature, when making its reflux 3 small.

《Production Example 4》

In the reactor for possessing agitating device, torque meter, nitrogen ingress pipe, thermometer and reflux cooler, POB is added 248.6g (1.8 moles), APAP 362.8g (2.4 moles), IPA 681.1g (4.1 moles), HQ 187.2g (1.7 moles) and Acetic anhydride 878.0g (8.60 moles).Will be in reactor fully with nitrogen into after line replacement, with 15 minutes under stream of nitrogen gas 150 DEG C are warming up to, keeps temperature, when making its reflux 3 small.

The manufacture ＞ of ＜ aromatic polyester films

《Embodiment 6》

The aromatic polyester powder 50g obtained in embodiment 1 is added in 1-methyl-2-pyrrolidinone 200g, is heated to 140 DEG C, as a result confirm and be completely dissolved and obtain transparent solution.The solution is stirred and deaeration, obtains fragrant adoption Ester solution.After solution obtained by being applied on copper foil with 200 μm of rods of coating thickness, using hot-air drier with 50 DEG C of heating 2 it is small when And solvent is removed, the further heat treatment with 300 DEG C of progress 1 when small in a nitrogen atmosphere.Lost from the copper foil of gained resin Carve and remove copper foil, that is, obtain the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Embodiment 7》

Using the aromatic polyester powder 50g obtained in embodiment 2 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Embodiment 8》

Using the aromatic polyester powder 50g obtained in embodiment 3 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Embodiment 9》

Using the aromatic polyester powder 50g obtained in embodiment 4 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Embodiment 10》

Using the aromatic polyester powder 50g obtained in embodiment 5 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Comparative example 1》

Using the aromatic polyester powder 50g obtained in Production Example 1 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Comparative example 2》

Using the aromatic polyester powder 50g obtained in Production Example 2 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Comparative example 3》

Using the aromatic polyester powder 50g obtained in Production Example 3 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

《Comparative example 4》

Using the aromatic polyester powder 50g obtained in Production Example 4 come instead of using the fragrant adoption obtained in embodiment 1 Ester powder, in addition, implements according to embodiment 6, obtains the aromatic polyester film with abundant intensity of 25 μm of film thickness.

Following such comment is carried out to aromatic polyester film (embodiment 6~10 and comparative example 1~4) obtained by operating as above Valency is tested.

1. thermal conductivity

Thermal conductivity (unit：W/ (mK)) by using the following method obtain thermal diffusivity (unit：m²/ s), specific heat it is (single Position：J/ (kgK)) and density (unit：kg/m³), and carry out the calculation of following formula and calculate.

Thermal conductivity=thermal diffusivity × specific heat × density

Here, on thermal conductivity, using temperature wave thermal analysis system under room temperature (such as 23 DEG C) to above-mentioned each aromatic series Polyester film is measured.As measurement device, the ai-Phase Mobile of ai-Phase company systems have been used.

On specific heat, using differential scanning calorimetry (DSC) (DSC), it is measured by the comparison with sapphire standard substance.

In addition, density is measured using Archimedes method.

2. tensile properties

According to JIS K7127, tensile strength and tension fracture elongation rate are measured.Using cupping machine with 5mm/min's Speed is stretched, and obtains intensity when sample blocks (fracture) (obtained by the sectional area of tensile load value divided by test film Value) and elongation.Tensile elongation is calculated by following formula.Tensile elongation is bigger, then it represents that film elongation is bigger.

Elongation (%)=(L-Lo)/Lo

Lo：Specimen length (mm) before experiment, L：Specimen length (mm) during fracture

By these evaluation tests, the results are shown in table 1.

[table 1]

As shown in table 1, the thermal conductivity of the aromatic polyester film of embodiment 6 is up to 0.31W/ (mK), tension failure elongation Rate is 26.4%, is good result.

As shown in table 1, the thermal conductivity of the aromatic polyester film of embodiment 7 is up to 0.30W/ (mK), tension failure elongation Rate is 22.0%, is good result.

As shown in table 1, the thermal conductivity of the aromatic polyester film of embodiment 8 is up to 0.29W/ (mK), tension failure elongation Rate is 27.5%, is good result.

As shown in table 1, the thermal conductivity of the aromatic polyester film of embodiment 9 is up to 0.29W/ (mK), tension failure elongation Rate is 24.8%, is good result.

As shown in table 1, the thermal conductivity of the aromatic polyester film of embodiment 10 is up to 0.30W/ (mK), tension failure elongation Rate is 22.3%, is good result.

The thermal conductivity of the aromatic polyester film of comparative example 1 is 0.27W/ (mK), is in a ratio of with embodiment 6~10 relatively low Value.Tension fracture elongation rate is 18.5%, less than embodiment 6~10, and less than 20%.

The thermal conductivity of the aromatic polyester film of comparative example 2 is 0.30W/ (mK), and 6~10 peer-level of embodiment, but Tension fracture elongation rate is 13.0%, less than embodiment 6~10, and less than 20%.

The thermal conductivity of the aromatic polyester film of comparative example 3 is 0.26W/ (mK), is in a ratio of with embodiment 6~10 relatively low Value.Tension fracture elongation rate is 16.2%, less than embodiment 6~10, and less than 20%.

The tension fracture elongation rate of the aromatic polyester film of comparative example 4 is 21.8%, and 6~10 peer-level of embodiment, But thermal conductivity is 0.23W/ (mK), and relatively low value is in a ratio of with embodiment 6~10.

Shown in evaluation result as more than, according to this embodiment, it can obtain the aromatic series that thermal conductivity is high, film elongation is big Polyester film.

Industrial applicability

According to the present invention it is possible to the aromatic polyester of film elongation and the excellent film of thermal conductivity can be formed, use by providing The aromatic polyester liquid composition of above-mentioned aromatic polyester, the manufacture method of aromatic polyester film and aromatic polyester film, Therefore it is industrially extremely useful.

Sign flag explanation

1 aromatic polyester film

Claims

1. a kind of aromatic polyester, as Component units, it includes：

(A) repetitive unit represented by following formula (a),

(B) repetitive unit in aromatic dicarboxylic acid source,

(D) repetitive unit in aromatic diol source；

Relative to (A) to (D) repetitive unit it is total,

-O-Ar¹-CO- (a)

In formula (a), Ar¹Represent 1,4- phenylenes, 2,6- naphthylenes or 4,4 '-biphenylene；Ar¹In represented group extremely A few hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl.

2. aromatic polyester according to claim 1, wherein, in the formula (a), Ar¹For 1,4- phenylenes or 2,6- Asias naphthalene Base.

3. aromatic polyester according to claim 1 or 2, wherein, the repetitive unit of (B) is following formula (b) institute table The repetitive unit shown,

-CO-Ar²-CO- (b)

In formula (b), Ar²Represent 1,4- phenylenes, 1,3- phenylenes, 2,6- naphthylenes or diphenyl ether -4,4 '-diyl；Ar²Institute's table At least one hydrogen atom in the group shown is optionally separately substituted by halogen atom, alkyl or aryl.

4. aromatic polyester according to claim 3, wherein, in the formula (b), Ar²For 1,4- phenylenes, 1,3- Asias benzene Base or 2,6- naphthylenes.

5. aromatic polyester according to any one of claim 1 to 4, wherein, the repetitive unit of (C) is following formula (c) repetitive unit represented by,

-X-Ar³-NH- (c)

In formula (c), Ar³Represent 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes；Ar³At least one in represented group A hydrogen atom is optionally separately substituted by halogen atom, alkyl or aryl；X expression-O- or-NH-.

6. aromatic polyester according to claim 5, wherein, in the formula (c), Ar³For unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 2,6- naphthylenes.

7. aromatic polyester according to any one of claim 1 to 6, wherein, the repetitive unit of (D) is following formula (d) repetitive unit represented by,

-O-Ar⁴-O-(d)

Ar⁴Represent 1,4- phenylenes, 1,3- phenylenes or 4,4 '-biphenylene；Ar⁴At least one hydrogen in represented group Atom is optionally separately substituted by halogen atom, alkyl or aryl.

8. aromatic polyester according to claim 7, wherein, in the formula (d), Ar⁴For unsubstituted, 1,4- phenylenes, 1,3- phenylenes or 4,4 '-biphenylene.

9. a kind of aromatic polyester film, it includes aromatic polyester described in any item of the claim 1 to 8.

10. a kind of aromatic polyester liquid composition, its contain aromatic polyester described in any item of the claim 1 to 8 and Non-protonic solvent.

11. aromatic polyester liquid composition according to claim 10, wherein, relative to 100 matter of non-protonic solvent Part is measured, containing more than 0.01 mass parts and 100 aromatic polyesters below mass part.

12. the aromatic polyester liquid composition according to claim 10 or 11, wherein, the non-protonic solvent is not The non-protonic solvent of halogen atom-containing.

13. the aromatic polyester liquid composition according to any one of claim 10 to 12, wherein, the aprotic The dipole moment of solvent is more than 3 and less than 5.

14. a kind of manufacture method of aromatic polyester film, it includes：

The process for making the aromatic polyester liquid composition any one of claim 10 to 13 be cast on supporting substrates； With

The process that solvent is removed from the aromatic polyester liquid composition on the supporting substrates.